• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Disclosed is a process for the production of lactic acid from glycerol using a catalyst selected from the group consisting of ruthenium, palladium and cobalt and / or mixtures thereof, and the process is carried out in an aqueous-basic medium.
    公开号:AT511965A4
    申请号:T14732011
    申请日:2011-10-11
    公开日:2013-04-15
    发明作者:Amitava Dipl Ing Dr Kundu
    申请人:Amitava Dipl Ing Dr Kundu；
    IPC主号:
    专利说明:

    The present invention relates to a novel process for the production of lactic acid.
    Lactic acid is an alkanoic acid having both a carboxy group and a hydroxy group and is also referred to as 2-hydroxypropionic acid and 2-hydroxypropanoic acid, their salts and esters are called lactates. Due to their different optical activity, D - (-) - lactic acid ((R) -lactic acid) is also referred to as levorotatory lactic acid and L - (+) - lactic acid ((S) -lactic acid) as dextrorotatory lactic acid. Racemic lactic acid is a 1: 1 mixture of (R) - and (S) -lactic acid. In 2010, about 250,000 tons of lactic acid were produced worldwide, which are mainly used in the food industry and for the production of polylactides (PLA).
    The production of lactic acid can be carried out both biotechnologically via a fermentation of carbohydrates (sugar, starch) as well as synthetically. Currently, nearly 95% of global lactic acid production is made available through relatively expensive and expensive fermentation of starch and glucose-containing agricultural products such as corn, wheat and sugar. In the fermentative production of a direct distillation to purify the resulting lactic acid by the also present sugar, protein and other impurities (acids, alcohols, esters, ...), however, considerably more difficult, the usual isolation based on the esterification to the corresponding methyl lactate , Distillation of the ester and subsequent hydrolysis. Synthetically, the production of lactic acid takes place by hydration of hydrogen cyanide (hydrocyanic acid, HCN). On the industrial scale, only the synthesis of lactic acid from acetaldehyde with hydrogen cyanide via lactonitrile plays a certain role. The latter is hydrolyzed by the use of hydrochloric acid, wherein in addition to the lactic acid ammonium chloride is formed. In recent years, the demand for lactic acid has been steadily increasing, and it will become an important commodity chemical because of its versatility. The benefits of lactic acid include complete biodegradability, C02 neutrality, and lactic acid polymers with the same processing capabilities as conventional fossil based plastics. In addition to the established use of lactic acid products in the cosmetics, pharmaceutical and food industries, the polymerized form PLA (polylactic acid) as a biodegradable plastic is one of the reasons for the increasing demand for lactic acid. The use of environmentally friendly, lactic acid-based organic solvents for the chemical industry is also growing rapidly.
    In the bio-diesel and fatty acid production, on the other hand, a glycerol-containing by-product is obtained, which is generally referred to as glycerol phase. The glycerol phase is usually a non-explosive, viscous, methanol-containing, dark liquid. In general, an attempt has been made for some time to provide the glycerol phase for recovery. Some studies have shown that the glycerine phase is good for the environment and can be used as a renewable energy source in the form of a supplementary, energizing fuel in biomass plants for the heat but also for electricity generation of local, regional and national households, commercial enterprises and industry. Due to the world-wide growing biodiesel and fatty acid production, the glycerol phase or glycerol separated from the glycerol phase is currently available in excess, which also accompanies a corresponding decline in the price of glycerol phase or glycerol.
    The prior art already has various documents relating to lactic acid and its preparation from glycerine. Thus, CN 101695657 A (Haichao Liu, Yihong Shen) describes a process for producing lactic acid using glycerine and specific catalysts. According to the description, the patented method proceeds under unspecified "mild conditions" using a platinum-based catalyst, also not described.
    US 2010/047140 relates to the conversion of glycerol to lactic acid under high temperature (340 ° C) and correspondingly high saturation vapor pressure (about 146 bar), optionally using calcium hydroxide as the catalyst. According to the examples, the glycerol concentration in the reaction solution is 0.33 M, and a relatively high yield was achieved with 80% as the best result.
    The process of CN101225041 allows the production of lactic acid at high pressure (up to 15 bar), temperatures up to 140 ° C and a reaction time up to 48 h the conversion of glycerol to lactic acid, however, only 12% to 70% at a selectivity of 33% 81% instead, the obtained lactic acid yield is very low at 9.7% to 32%.
    CN 101255451, US 2009/104675 and JP 2009050251 all describe a fermentation process using glycerol.
    The chemical conversion of glycerol to lactic acid is also described in publications and textbooks, for example in Yuksel, A .; Koga, H .; Sasaki, M .; Goto, M. Electrolysis of glycerol in subcritical water. J. Renewable Sustainabte Energy 2009, 1, 033112. The method described is based on a hydrothermal electrolysis at a glycerol concentration of 0.1 M and a temperature of 280 ° C, with a lactic acid yield of 34.7% was achieved.
    Kishida, H .; Jin, F .; Zhou, Z .; Moriya, T .; Enomoto, H. Conversion of glycerol into lactic acid by alkaline hydrothermal reaction, Chem. Lett. 2005, 34, 1560-1561 and Shen, Z .; Jin, F .; Zhang, Y .; Wu, B .; Kishita, A .; Kishida, H. Effect of alkaline catalysts on hydrothermal conversion of glycerol into lactic acid. Ind. Eng. Chem. Res. 2009, 48, 8920-8925, however, report a yield of up to 90%, but the reaction conditions at 300 ° C and a required reaction pressure of 90 bar are very energy-intensive and thus the associated operating costs obviously higher than that of aforementioned method. Also, the disclosed glycerol concentration of 0.33 M is generally uneconomical for industrial applications due to the associated low productivity and the required energy consumption.
    Ramirez-Lopez, C.A .; Ochoa-Gomez, J.R .; Fernandez-Santos, M .; Gomez-Jimenez-Aberaturi, O; Alonso-Vicario, A .; Torrecilla-Soria, J. Synthesis of Lactic Acid by Alkaline Hydrothermal Conversion of Glycerol at High Glycerol Concentration. Ind. Eng. Chem. Res. 2010, 49, 6270-6278, describes a process which builds on the two aforementioned, but the glycerol concentration in the reaction solution with 2.5 M is considerably higher. However, the reported yield of 84.5% is also achieved under very high temperatures (280 ° C) and high pressure.
    The object of the present invention is now to provide a process whereby glycerol can be converted under the simplest possible conditions into lactic acid with a high yield. This object is achieved in accordance with the invention by the use of a catalyst selected from the group consisting of ruthenium, palladium and cobalt and / or mixtures thereof in an aqueous-basic medium. Preferably, the catalyst (s) are / is used in the form of its oxide, hydroxide or metal, most preferably the hydroxide and the elemental metal are supported. The catalyst (s) may optionally be provided on one or more suitable supports, which supports are preferably selected from the group consisting of carbon, activated carbon, Al 2 O 3, Fe 3 O 4, Fe 2 O 3, TiO 2, hydroxyapatite and / or mixtures thereof. The process according to the invention was developed especially for use in biodiesel plants and can also be subsequently integrated into already existing production plants, thereby making it possible for biodiesel producers to process any residues themselves to lactic acid. The main reaction product in the process according to the invention is sodium lactate. Sodium formate and propylene glycol occur, inter alia, as by-products (depending on the catalyst used, ruthenium catalysts contain larger amounts of formate than in the reaction with palladium catalysts, where formate is only present in trace amounts)
    Particularly preferred, when the catalyst is selected from the group comprising Ru (OH) x / Fe304, Ru (0H) x / Fe203, Ru (OH) x / TiC> 2, Ru (OHyAl203, Ru (OH) x / HAp (RuHAp: ruthenium hydroxyapatite), Ru / activated carbon, RuCl3 * nH20, Pd / C, Pd / activated carbon, Pd (OH) 2 / activated carbon, Pd (0H) x / Fe3O4, Pd / Fe304, PdCl2, co-silicide ( CoSi2), Ru (OH) x-Pd (OH) x / Fe304, Ru-Pd / Fe304, Ru (OH) x-Co / Fe304, Co-Pd (OH) x Fe304, and mixtures of Ru / activated carbon and Pd / Activated carbon or Ru / activated carbon and Pd (OH) 2 / activated carbon catalysts have proven to be most stable on charcoal carriers, which could be quantitatively recovered and used several times without loss of activity, with Pd / Ru mixed catalysts.
    According to a preferred embodiment of the present invention, the catalyst (s) is / are used in a concentration of 1.25% -5% 5 (based on the active catalyst metal), more preferably a concentration of 2.5%.
    Preferably, in the method according to the invention, a glycerol concentration of more than 4 M is provided, ie a much higher concentration than described in the literature or other patents. The more concentrated the reaction volume the smaller the reactor size (low volume) and the lower the reaction and processing costs, since less energy must be applied to heat the reaction and then distilling off the water. Of course, lower glycerol concentrations are also suitable. In the currently conventional fermentative production of lactic acid, the reaction is carried out in comparatively high dilutions, which requires large reactors and a high energy expenditure in the isolation of the product, since a great deal of water has to be removed. The low reaction volume makes it possible to implement the necessary reactors directly in biodiesel plants. The inventive method further allows due to fewer by-products, a direct and thus cost-effective distillation of lactic acid in vacuo. It is also advantageous if crude glycerol is used directly in the process according to the invention, which eliminates purification steps, which contributes to the economy of the method. For example, the glycerol phase from a biodiesel or fatty acid preparation can be used as crude glycerol.
    It is particularly preferred if the aqueous-basic medium comprises 1.7-2 eq base. At a glycerol concentration of 5 M, for example, this is a 13.4 M solution, with NaOH preferably being used as the base. More NaOH causes higher reaction costs; less NaOH delays the full turnover. Instead of NaOH, other bases are also suitable, e.g. KOH.
    The following examples serve to explain the process according to the invention in more detail, but without limiting it.
    In general, the editorial procedure in the experiments for the method according to the invention was carried out such that the catalyst is placed in a flask and glycerol (including crude glycerol) and the basic solution (NaOH, KOH) are added. Subsequently, the reaction suspension is stirred for about 1 h by means of a magnetic stirrer and the evolution of hydrogen is awaited. Thereafter, the suspension is heated by means of oil bath to 100 ° - 110 ° C and stirred for 10 - 14 h under slight reflux, which condenses from submitted basic solution and water formed during the reaction at the reflux condenser. During this time H2 continues to escape. After the reaction time, the reaction suspension is cooled to room temperature and the conversion determined by NMR. The main reaction product is sodium lactate, sodium formate and propylene glycol occur as by-products, depending on the catalyst used.
    For workup, the heterogeneous catalyst is separated by filtration or centrifugation (in the case of magnetic catalysts also with magnetic separation). The pH of the remaining solution is adjusted from strongly basic to about pH 2 by means of acid (HCl, H 2 SO 4). The sodium lactate (and the formate) formed in the reaction is hydrolyzed and free lactic acid is present. Optionally, precipitated salts can be filtered off. The use of HCl provides a good method to acidify the reaction solution. In the subsequent distillation, the hydrochloric acid is completely removed and no longer disturbs the process of isolation of lactic acid. The use of sulfuric acid is also suitable, but involves the risk of the formation of lactic acid oligomers, since after the removal of water, acid is still present and thus a lactic acid esterification is promoted. The lactic acid is then isolated from the acidified solution by means of vacuum distillation: water, formic acid and propylene glycol evaporate at 2 mbar even at low temperature (these substances may optionally be fractionally distilled even at lower vacuum). At 88 ° -90 ° C, lactic acid is distilled. A stronger vacuum (e.g., 1 mbar or less) allows distillation at correspondingly lower temperatures (at 1 mbar, about 80 ° C). Lactic acid still remaining in the distillation residue can be extracted by a suitable extractant (eg isopropanol, butanol, methyl tert-butyl ether, diethyl ether and the like) in which lactic acid, but not the resulting salt, is soluble and then isolated by redistillation , The sodium chloride produced by the neutralization remains behind. Alternatively, the lactic acid liberated by acidification can be removed immediately with the aid of an extractant. Following this, after removal of the extractant, the product is then isolated by vacuum distillation.
    Besides the direct distillation of the free lactic acid, isolation by means of esterification with alcohol (eg methanol, ethanol and the like) is also possible. For this purpose, after the acidification of the reaction suspension, the lactic acid is esterified and distilled off. Subsequent hydrolysis releases the lactic acid, by stripping off the alcohol, the remaining lactic acid is isolated.
    Examples:
    Example 1 0.34 g of Pd (OH) x-Ru (OH) x / Fe304 catalyst (1 mmol / g loading, 0.34 mmol) are placed in a one-necked flask and 1 ml (1.26 g; 68 mmol) of glycerol and 1.74 ml of an aqueous solution of 0.93 g of NaOH (13.36 M 23.25 mmol) are added. Subsequently, the reaction suspension is stirred for about 1 h (magnetic stirrer) and the evolution of hydrogen is awaited. Thereafter, the suspension is heated by means of oil bath to 100 ° - 110 ° C and stirred for 10 - 14 h with gentle reflux, during this time escapes further H2. After the reaction time, the reaction suspension is cooled to room temperature and the conversion determined by NMR, it was 77%.
    Example 2 0.347 g Ru0Hx / Fe304 catalyst (loading: 1 mmol / g, 0.347 mmol) are placed in a one-necked flask and 1 ml (1.26 g, 13.68 mmol) glycerol and 1.74 ml of an aqueous solution of 1.307 KOH (13.39M, 23.29mmol) is added. Subsequently, the reaction suspension is stirred for about 1 h (magnetic stirrer) and the hydrogen evolution is awaited. Thereafter, the suspension is heated by means of oil bath to 100 ° - 110 ° C and stirred for 10 - 14 h with gentle reflux, during this time escapes further H2. After the reaction time, the reaction suspension is cooled to room temperature and the conversion determined by NMR, it was 60%.
    8th
    Example 3
    A mixture of 0.35 g of Ru / activated carbon (5% loading, 0.171 mmol) and 0.24 g of Pd (OH) 2 / activated carbon (20% loading, 50% H2O, 0.171 mmol) are placed in a one-necked flask and 1 ml Crude glycerine (glycerine content: 80%, 10.94 mmol, from a glycerol phase, provided by an Austrian biodiesel producer) and 1.74 ml of an aqueous solution of 0.93 g NaOH (13.37 M, 23.26 mmol) added. Subsequently, the
    Reaction suspension stirred for about 1 h (magnetic stirrer) and the evolution of hydrogen was awaited. Thereafter, the suspension is heated by means of oil bath to 100 ° - 110 ° C and stirred for 10 - 14 h with gentle reflux, during this time escapes further H2. After the reaction time, the reaction suspension is cooled to room temperature and the conversion determined by NMR, it was 79%.
    Example 4
    For workup, the heterogeneous catalyst from the reaction solution of Example 1 is separated by filtration, with H2Odest. washed and adjusted the pH of the remaining slightly diluted solution by means of HCl (12 M) to about pH 2. The lactic acid is separated by vacuum distillation (Kugelrohr) at 2 mbar and 88-90 ° C, the yield was 0.643 g (52%). A further yield of lactic acid was obtained by extraction 4 times (7 ml each, stirred for about 1 h) by means of isopropanol from the distillation residue and, after isolation by redistillation, gave a further 0.256 g (21%).
    Example 5
    For workup, the heterogeneous catalyst from the reaction solution of Example 3 is separated by filtration, with H2Odest. washed and the water removed by rotary evaporator. The residue was then dissolved in 6 ml of MeOH, the pH of the solution was adjusted to about pH 2 with H 2 SO 4 (9 M) and esterified under reflux (of the methanol) for 4 h. The resulting methyl lactate was isolated by fractional distillation from the remaining components (including methanol, water) at 30 mbar and about 55 ° -60 ° C. Subsequent hydrolysis of the methyl lactate using 4 ml H2Odest and heating to 70 ° C for 9 h set the * * * 4 * * *·· * * * * * # * 9
    Lactic acid free. Methanol and water were removed at 40 ° C under reduced pressure. The yield of lactic acid was 0.620 g (63%).
    Chemicals Used RuCI3 nH20 (n = 3): Johnson Matthey, Switzerland Fe203 (99%; <5 micron): Sigma-Aldrich, Germany Fe304 (98%; <5 micron): Sigma-Aldrich, Germany AI2O3 (AI2O3 90 Grain size 0.063 - 0.2 mm): Merck Germany Ti02 (1/8 "pellets, 1% S) Alfa Aesar, Germany Co silicide (99%): Alfa Aesar, Germany Co (OH) 2 (99.9%) Alfa Aesar, Germany Pd (OH) 2 / C (20%, 50% H 2 O): Aldrich, Germany Pd / C (10%): Aldrich, Germany Pd / charcoal (10%): Aldrich, Germany NaOH (min. 99%): Sigma-Aldrich, Germany CoCI2 (97%): Aldrich, Germany NaBH4 (12 wt% in 14M NaOH): Aldrich, Germany Pd (OAc) 2 (98%): Aldrich, Germany Hydroxyapatite (reagent grade ^) 7%): Aldrich, Germany KOH (90%): Sigma-Aldrich, Germany PdCI2 (99%): Aldrich, Germany
    Propan-2-ol (99.5%) Fischer Scientific, UK
    权利要求:
    Claims (14)
    [1]
    A process for the production of lactic acid from glycerol, characterized in that a catalyst selected from the group consisting of ruthenium, palladium and cobalt and / or mixtures thereof is used and the process is carried out in an aqueous-basic medium.
    [2]
    2. The method according to claim 1, characterized in that the / the catalyst / s in the form of its oxide, hydroxide or metal is / are used.
    [3]
    3. The method according to claim 1 or 2, characterized in that the / the catalyst (s) is / are used in the form of its hydroxide.
    [4]
    4. The method according to claim 1 or 2, characterized in that the / the catalyst / s is used in metallic form / are.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that the / the catalyst / s is provided on one or more suitable carriers / are.
    [6]
    6. The method according to claim 5, characterized in that the carriers are selected from the group consisting of carbon, activated carbon, Al203, Fe304, Fe203, Ti02, hydroxyapatite and / or mixtures thereof.
    [7]
    7. The method according to claim 6, characterized in that the / the catalyst / s is provided on activated carbon / are
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the / the catalyst (s) is / are selected from the group comprising Ru (OH) x / Fe304, Ru (0H) x / Fe203! Ru {0H) x / TiO 2, Ru (0H) x / Al 2 O 3, Ru (OH) x / HAp (RuHap: ruthenium hydroxyapatite), Ru / activated carbon, RuCl 3 * nH 2 O, Pd / C, Pd / activated carbon, Pd (OH ) 2 / charcoal, Pd (0H) x / Fe304, Pd / Fe304, PdCl2, co-silicide (CoSi2), Ru (OH) x-Pd (OH) x / Fe304) Ru-Pd / Fe304, Ru (OH) x-Co / Fe304, Co-Pd (OH) x Fe304, and mixtures of Ru / activated carbon and Pd / activated carbon or Ru / activated carbon and Pd (OH) 2 / activated carbon. • * * * · «·
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that the / the catalyst / s in a concentration of 1.25% - 5% based on the active catalyst metal is / are used.
    [10]
    10. The method according to claim 9, characterized in that the / the catalyst (s) is / are used in a concentration of 2.5% based on the active catalyst metal.
    [11]
    11. The method according to any one of claims 1 to 10, characterized in that a glycerol-containing solution having a glycerol concentration of more than 4 M is provided as starting material.
    [12]
    12. The method according to any one of claims 1 to 11, characterized in that as raw material raw glycerol, optionally in the form of a solution is provided.
    [13]
    13. The method according to claim 12, characterized in that as the starting material, the glycerol phase is provided from a biodiesel or fatty acid production.
    14. The method according to any one of claims 1 to 13, characterized in that the aqueous basic environment comprises 1.7 - 2 eq base. A process for the production of lactic acid from glycerol, characterized in that a catalyst selected from the group consisting of ruthenium, palladium and cobalt and / or mixtures thereof and the method at atmospheric pressure in aqueous basic environment. 2. The method according to claim 1, characterized in that the / the catalyst / s in the form of its oxide, hydroxide or metal is / are used. 3. The method according to claim 1 or 2, characterized in that the / the catalyst (s) is / are used in the form of its hydroxide. 4. The method according to claim 1 or 2, characterized in that the / the catalyst / s is used in metallic form / are. 5. The method according to any one of claims 1 to 4, characterized in that the / the catalyst / s is provided on one or more suitable carriers / are. 6. The method according to claim 5, characterized in that the carriers are selected from the group comprising carbon, activated carbon, Al2O3, Fe304, Fe203, Ti02, hydroxyapatite and / or mixtures thereof. 7. The method according to claim 6, characterized in that the catalyst (s) is / are provided on activated carbon 8. The method according to any one of claims 1 to 7, characterized in that the / the catalyst / s / is selected from the Group comprising Ru (OH) x / Fe304, Ru (0H) x / Fe2O3, Ru (0H) x / TiO2, Ru (0H) x / Al2O3, Ru (OH) x / HAp (RuHap: ruthenium hydroxyapatite), Ru / Activated carbon, RuCl3 * nH20, Pd / C, Pd / activated carbon, Pd (OH) 2 / activated carbon, Pd (0H) x / Fe304, Pd / Fe304, PdCl2, co-silicide (C0S12), Ru (OH) x- Pd (OH) x / Fe304, Ru-Pd / Fe304, Ru (OH) x-Co / Fe304, Co-Pd (OH) x Fe304, and mixtures of Ru / activated carbon and Pd / activated carbon or Ru / activated carbon and Pd (OH) 2 / charcoal. 9. A process according to any one of claims 1 to 8, characterized in that the catalyst (s) is / are used in a concentration of 1.25% to 5%, based on the active catalyst metal , 10. The method according to claim 9, characterized in that the / the catalyst (s) is / are used in a concentration of 2.5% based on the active catalyst metal. 11. The method according to any one of claims 1 to 10, characterized in that a glycerol-containing solution having a glycerol concentration of more than 4 M is provided as starting material. 12. The method according to any one of claims 1 to 11, characterized in that as raw material raw glycerol, optionally in the form of a solution is provided. 13. The method according to claim 12, characterized in that as the starting material, the glycerol phase is provided from a biodiesel or fatty acid production.
    [14]
    14. The method according to any one of claims 1 to 13, characterized in that the aqueous basic environment comprises 1.7 - 2 eq base. SUBSEQUENT
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    引用文献:
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    CN101695657B|2009-10-27|2012-10-10|北京大学|Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin|CN106810436B|2015-11-30|2020-06-30|中国科学院大连化学物理研究所|Method for preparing lactic acid by catalytic oxidation of glycerol|
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    CN109174183A|2018-08-28|2019-01-11|东北师范大学|The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol|
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    法律状态:
    2016-02-15| PC| Change of the owner|Owner name: AB&CD INNOVATIONS GMBH, AT Effective date: 20160111 |
    2021-06-15| MM01| Lapse because of not paying annual fees|Effective date: 20201011 |
    优先权:
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    AT14732011A|AT511965B1|2011-10-11|2011-10-11|PROCESS FOR THE PREPARATION OF MILKY ACID|AT14732011A| AT511965B1|2011-10-11|2011-10-11|PROCESS FOR THE PREPARATION OF MILKY ACID|
    ARP120103750| AR089170A1|2011-10-11|2012-10-09|METHOD FOR THE PRODUCTION OF LACTIC ACID|
    PCT/AT2012/000260| WO2014056005A1|2011-10-11|2012-10-11|Method for producing lactic acid|
    UY34386A| UY34386A|2011-10-11|2012-10-11|Method for the production of lactic acid|
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